Chelating monomers and polymers



United States. Patent 3,090,771 Patented May 21, 1963 This invention concerns new chelating monomers and polymers and methods for making the new monomers and polymers. Broadly, this invention deals with polymerizable organic compounds having the formula T and their polymers containing repeating units of the structure .I wherein Am is aliphatic aminooarboxyl acid radical bonded through a nitrogen atom, R represents hydrogen and methyl, R represents hydrogen and lower alkyl radicals of 1 to 6 carbon atoms, K is a divalent alkylene radical of l to 8 carbon atoms in the linear chain between said valencies and preferably represents a total of no more than about 16 carbon atoms, Ar represents a divalent aromatic hydrocarbon radical and the chloro and fluoro derivatives thereof.

Specifically, this invention is directed to the syntheses of these new monomers and to polymerization products obtained by polymerizing a mass comprising these new monomer compounds in the presence or absence of other polymerizable ethylenic compounds. It is a particular object of this invention to prepare soluble and insoluble polymers having in the polymer molecule a plurality of repeating units having the formula also given above. It is a still further object of invention to prepare new monomeric and polymeric compounds capable of chelating metal ions and to provide a method for making such monomers and polymers.

Heretofore, certain chelating monomers containing a vinyl aryl nucleus have been prepared by reacting a vinylaryl benzyl halide with an aminoaoid, and this synthesis is dependent on the expensive and difiiculty prepared vinylbenzyl chloride. Another synthesis involves the reaction of chloroacetic acid with vinylbenzyl amine which is synthesized from the vinylbenzyl halide. A third synthesis is even more expensive, involving the use of vinylbenzaldehyde.

I have now discovered that chelating monomers having a vinylaryl nucleus can be prepared from readily available alkenyl aryloxyepoxyalkanes of the formula,

CH1=GRAr-O (OHR) DOB-CR:

o e.g. 1-vinylphenoxy-2,3-epoxypropane OHz=OHCaH40OH:CHCH2 by the simple reaction with a compound possessing an active hydrogen and having chelatin-g properties, for example, an amino acid, more particularly an imino acid, e.-g.,

CH=CHOH;OCHQ\H/CH1 NH(OH;OOOM)2 O GHFCHCsEhOCHzfiJH-OHaNKlHzCOOM):

and/or CH =CHOuH4O CHzCHOHzOH memo 0 0M): which is generalized as l cm=ono.H.ooH,oH-orn l l j-N( 2CO OM 2 wherein M is a hydrogen, a lower alkyl or aryl group,

an ammonium base, or a metal; and that these monomers can be polymerized and copolymerized with each other and with other monomers.

I have discovered further that I can first polymerize or copolymerize the alkenylaryloxyepoxy-allcane to a polymer product having a plurality of repeating of the formula 1 HN(CH2COOM)2 N (CHzCOOM) 2 The aliphatic aminocarboxylic acids can be represented by H-Am wherein Am represents an aliphatic aminoacid radical attached to the hydrogen radical through the nitrogen atom.

As is well known, the conventional ion exchange resins are incapable of recovering heavy metal ions firom solution containing a higher concentration of allcaliand alkaline-earth ions because such resins function solely by ion-exchange involving electrovalent bonds, and their performance is determined by mass action laws.

It will be noted that the opening of the epoxide linkage results in a hydroxy group which is hydrophilic in character and assists in the wetting of the polymer, especially if it is crosslinked, by aqueous solution of metal cations. Illustrative aromatic groups represented by Ar include,

lllustrative examples of the amino acids, H-Am, which can be reacted with alkenylaryloxyepoxyallcanes are glycine, NH CH COOH; alanine, CH CH(NH )COOH; serine, HOCH CH(NH )COOH; cystene HSCH CH(NH CO OH aminobutyric acid, CH CH CH(NH )COOH; threonine CH CH(OH)CH(NH COOH; valine (CH CHCH(NH )COOH 3 norvaline, CH CH CH CH(NH CO OH; isovlaline,

H3 C H: NH:

CH3 methionine, CH SCH CH CH (NH COOH; (CH CHCH CH(NH COOH; norleucine neucine,

phenylalanine, C H CH CH (NH COOH; aspartic acid NET-CH. C O O H CH2O 0 0H glutamic acid NHz (EH-C O O H (1313: CH2 C O O H lysine, NH (CH CH(NH )COOH; 1,2-diamino propionic acid ITIIEI: NHzCHnCH-C O OH aminopimelic acid, HOOC(CH CH(NH )COOH; betaaminovaleric acid, CH CH CH(NH )CH COOH; hydroxylysine hydroxyethylglycine, I-IOCH CH NI-ICH COOH; aminoethylglycine, NH CH CH NHCH COOH; iminoacetic acid, NH(CH COOH) iminopropionic acid NH (CH CH CO OH) 2 aminoethyliminoacetic acid N H CH CH N (CH COOH) 2 aminopropylirninoacetic tacid NH (CH N(CH COOH) HzCOOH etc., to give the polymerizwable monomers of this invention. Instead of the free acid, or the ammonium bases, or the metal bases, the lower alkyl or aryl esters of the aforementioned amino acids also can be used and the reaction product hydrolyzed to obtain the acid.

Instead of reacting the monomric alkenylaryloxyepoxyalkanes with an amino acid, I can first polymerize the alkenylaryloxyepoxyalkanes by vinyl (double bond) polymerization and react the polymer with the amino acid. In either case, when either the monomer or polymer is reacted with the amino acid and the resulting product has an amino group still possessing unsubstituted hydrogen or hydrogens, such compounds can react further with chloroacetic acid or with glycolic nitrile, HOCH CN (or its equivalent, an aldehyde and hydrogen cyanide), to introduce further CH COOM groups in the compound.

As is well known the oxirane ring is opened readily by amines and acids and this behaviour offers alternate, though not the preferred, syntheses for the monomers and em -4 in polymers of this invention. For example, an alkenylaryloxyepoxyalkane reacts readily with HCl to give a chlorohydrin which in the presence of alkali reacts with the aforementioned amino acids to give the monomers of this invention; and the corresponding vinyl polymer behaves in the same manner, thus,

Or, the'alkenylaryloxyepoxyalkane can be reacted first with ammonia or a primary amine to give a substituted alkanolamine and thereafter converted to an amino acid in the normal manner with a haloacetic acid or with a mixture of an aldehyde and an inorganic cyanide, thus CHFCH CHFCH and the corresponding polymer behaves in a similar manner, e.g.,

Because of costs and other economic factors, I prefer for the practice of this invention, compounds of the formula R g -NZ CH1: 0,1140 omoHoH .I wherein Z represents a radical selected from the group of RI! omooorr, rmooom, CHnOHzOOOM, OHCOOM moooM --(OH:) .Nrv'cmo 0 0M, -0 ,)N 0H,00 0M):

If}!!!a (OHQMCH-COOM, (OHQnCHOOOM moooM N OH 0001 R f 2 VI): I l CH1 CHCOOM CHa=CCsH4O CHzCHCHg wherein M is a member of the group consisting of hydrogen, lower alkyl and aryl groups, ammonium bases, and metals, n is an integer of 1 to 10, R represents hydrogen and methyl, and R" represents a radical selected from the class of hydrogen, lower alkyl radicals, lower hydroxyalkyl radicals, lower mercaptoalkyl radicals, lower aryl radicals, and K-COOM.

Some of the compounds of this invention can be represented also by the following formula:

[OHg=OR'Ar-OK'CRGR2 l l --NK(NR"-OHR")n'CO0M wherein the symbols Ar, K, R, R, R", and M are as defined above; 11' is 0 or 1; R'" is a group represented by R" and can also be and K is a divalent alkylene group preferably having no more than about carbon atoms in the chain connecting said valencies.

It is preferred that, when n is 0, either K represents a methylene or ethylene group or there is an NR", group substituted on a carbon atom of K no farther removed than two carbon atoms from said COOM group. The alkylene radical K can have substituted thereon various substituent groups, such as OH, NR SH, lower alkyl-S groups, and lower aryl groups, as well as additional COOM groups. The simpler compounds are preferred, generally those derived from amino acids having no more than about 20 carbon atoms therein, preferably no more than about 10 carbon atoms, and advantageously having no more than about two groups selected from the class consisting of hydroxy and thio groups. Also, it is generally not any particular advantage to have more than six groups in the amino acid selected from the class consisting of amino and COOM groups.

As used herein, the terms lower alkyl, lower hydroxyalkyl, lower mercaptoalkyl, and lower aryl are intended to include such groups having no more than about 10 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, amyl, secondary amyl, hexyl, heptyl, nonyl, decyl, secondary hexyl, secondary nonyl, benzyl, phenethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxyamyl, mercaptoethyl, mercaptomethyl, mercaptopropyl, mercaptoamyl, methylmercaptomethyl, methylmercaptoethyl, ethylmercaptomethyl, ethylmercaptoethyl, ethylmercaptopropyl, phenyl, tolyl, dimethylphenyl,

naphthyl, ethylphenyl, propylphenyl, butylphenyl, etci groups.

The ammonium bases defined herein for M include the ammonium radical and various substituted ammonium radicals having various substituents thereon, such as alkyl groups, aryl groups, hydroxyalkyl groups, etc., preferably those having no more than about 21 carbon atoms, advantageously those having no more than about 10 carbon atoms. Typical examples of such substituted ammonium radicals include those derived from ammonia, methyl amine, dimethyl amine, trimethyl amine, ethyl amine, diethyl amine, triethyl amine, propyl amine, butyl amine, dibutyl amine, tributyl amine, trihexyl amine, triheptyl amine, ethanol amine, diethanol amine, triethanol amine, isopropanol amine, diisopropanol amine, triisopropanol amine, methyl diethanol amine, dimethyl ethanol amine, morpholine, dimethyl benzyl amine, pyridine, ethyl pyridine, quinoline, isoquinoline amino pyridine, guanidine, biguanidine, aniline, methyl aniline, dimethyl aniline, phenylene diamine, piperazine, triethylene diimine CHQCH:

(N-OHzGHz-N) CHgCHg hydrazine, methyl hydrazine, symmetrical dimethyl hydrazine, phenyl hydrazine, amino imidazole, amino diazines, hydrazino triazines, etc.

Typical metals that can be used in substitution for M in the formulas given herein, include lithium, sodium, potassium, rubidium, cesium, calcium, strontium, barium, and the chelate-forming metals as disclosed in Chemistry of Metal Chelates, by Martell and Calvin, published by Prentice-Hall (1956). Page 182 of this book shows the periodic classification of chelate-forming metals.

The monomers of this invention can be polymerized individually or as mixtures with each other, or with 0.1, preferably 1 percent by weight or more of other vinyl and vinylidene compounds, such as styrene, alphamethyl styrene, vinyl toluene, vinyl xylene, chlorostyrene, butadiene, isoprene, acrylonitrile, methacrylonitrile, methacrylate, ethylacrylate, benzylacrylate, methyl methacrylate, ethyl methacrylate, glycol diacrylate, glycol dimethacrylate, allyl acrylate, allylmethacrylate, vinyl acetate, vinyl propionate, diallyl succinate, diallyl phthalate, maleic anhydride, dimethyl maleate, itaconic anhydride, itaconic imide, dimethyl itaconate, diallyl itaconate, acrylamide, methacrylamide, allylacrylamide, hydroxyethylacrylamide, N-methylene-bis-acrylamide, acetylglycine, vinyl pyridine, methacrylyllysine, methylvinylketone, acetylaminophenylethylene, vinylimidazole, 2-isopropenyl-4-isopropyl 2 oxazolin 5 one, N-vinyl 5 methyl 2 oxazolidinone, N-vinyl-pyrrolidone-Z, etc., or they can be grafted to other polymers containing peroxy groups to produce grafted copolymers, as disclosed in my copending application, Serial No. 28,560, filed the same date herewith.

The polymers and copolymers of this invention can be prepared in mass, in solution, in suspension, and emulsion systems, using the accepted initiating systems, such as the per compounds that generate radicals, or thermally, or with ultraviolet light, or with ionizing radiation, and in some cases, with ionic catalysts, both cationic and anionic, e.g., BF sodamide, HF, etc.

The invention is illustrated by the following examples which are intended merely for illustration and are not in any way to be interpreted as limiting the manner in which the invention can be practiced. All parts and percentages are given by weight unless otherwise specified.

EXAMPLE I To a mixture of 1000 parts of water, 1500 parts CH OH, 81 parts NaOH in 500 parts water and 133 parts of iminodiacetic acid in a suitable reaction flask equipped with a stirrer and heating means, there is added slowly at 35 C. over a period of two hours, 176 parts of 1-(4- 7 vinylphenoxy)-2,3-epoxypropane, following which the mixture is refluxed for /2 hour. The methanol then is distilled from the reaction mixture and 10 parts of decolorizing carbon stirred into the reaction mixture and the mixture filtered. The cooled, filtered mixture is acidified with concentrated hydrochloric acid to a pH of 23 and the white crystalline precipitate collected by filtration, dried, and there is obtained a monomer corresponding to the formula on,=onoflmoomonom I a momoooH):

which, an elemental analysis, gives C, 58.20%; H, 6.21%; N, 4.48%, which values are in close agreement with the theoretical.

Reaction with bromine confirms the presence of'olefin unsaturation.

The monomer of this example is characterized further by its ability to chelate metal ions in solution. The.

metal chelates are prepared by dispersing the sodium or ammonium derivative of monomer compound in water, or in an N KCl or NaCl solution and adding the metal ion in the form of a salt, such as the nitrate, chloride, sulfate, etc., e.g. CuCl FeC1 FeCl etc; or the acidic monomer compound can be used directly by dispersing it in the solution of the metal ions and adding alkaline substances, such as NaOH', KOH, LiOH, NH CH NH (CH3)2NH, (CH3)3N, etc. The mOI1-. omer of this example forms 1:1, and 2:1 chelates with CuH, CO++, Ni++, Fe+++, Fe++, P-b++, as well as a 1:1 chelate with Mn++.

EXAMPLE II The procedure of Example I is repeated using 117 parts of isovaline and 41 parts of NaOH instead of the iminodiacetic acid and 81 parts NaOH. There is obtained a monomer corresponding to the formula on 0110110011 CHOH I I: F H I-on omen,

which on analysis gives C, 65.89%; H, 7.22%; N, 4.78%, which values are in close agreement with the theoretical.

EXAMPLE III When 117 parts of valine are used in the procedure of Example H instead of isovaline, there is obtained a monomer corresponding to the formula,

of Example II instead of isovaline, there is obtained a monomer corresponding to the formula,

which on elemental analysis gives values for C, H, and

N in close agreement with the values of Example IH.

,EXAMPLE V I When the procedure of Example II is repeated using an equivalent amount of (a) 75 parts glycine, (b) 89 parts alanine,

parts leucine, and (e) 151 parts phenyl glycine, respecin good agreement 103 parts aminobutyric acid, (d) 165.

tively, in place of the isovaline, there is obtained respec tively, monomers corresponding to the formulas which on analyses give values for C, H, and N in close agreement with the theoretical values for these compounds, and which have good chelating, properties for metal ions.

EXAMPLE VI 7 The procedure of Example I is repeated using 133 parts of aspartic acid instead of iminodiacetic acid and there is obtained a monomer corresponding to the formula whose chelating properties are similar to the monomer of Example I.

EXAMPLE VII When 147 parts of glutamic acid are substituted for the aspartic acid of Example VI, there isobtained a monomer corresponding to the formula om=orro.n,oomoH-cm I TNH-CHC 0 OH HzCHzCOOH and when parts of aminopimelic acid are used instead of the aspartic acid of Example VI, there is obtained a monomer corresponding to the formula or: CH CHC H4OCHgOHOHg I 1 I NHCHOO0H 7 CHaCHaCHaQHaCOOH which has marked chelating properties for metal ions.

EXAMPLE VIII 5 '146 parts of 1-(4-vinylphenoxy) -2,3-epoxypropane are reacted with 149 parts of methionine and 41 parts NaOH in a water-methanol solution according to the procedure of Example I and there is obtained a monomer corresponding to the formula l CH=CHCaIELgO omen-0H, I V

,, 1 1 TNHOHGOOH CHgCHzSCHa EXAMPLE IX When the procedure of Example VHI is repeated using 119 parts of hydroxyethyl glycine instead of methionine, there is obtained a monomer corresponding to theformula;

When evaluated by the procedure of Example I, the monomers of Examples H and XII inclusive are shown to form metal chelates with heavy metal ions in solution.

HCHzOH EXAMPLE XIII 181.5 parts of vinylphenoxyglycerylchlorohydrin, EXAMPLE X When the procedure of Example VIII is repeated using H Y LL 104 parts of serine instead of methionine there is obtained a compound corresponding to the formula (obtained by reacting one mole of 1-vinylphenoxy-2,3- l g epoxypropane with one mole of concentrated HCl solu- OHz=0HC6H40 2J tion) are added slowly over a period of 90 minutes to a l refluxing stirred mixture in a suitable reactor of 133 parts HIGH of iminodiacetic acid, 81 parts of NaOH, 1000 parts of water and 2000 parts of methanol. After half of the chlorohydrin has been added, another 40 parts of NaOH EXAMPLE XI in 150 parts of water is added, and the addition of the chlorohydrin continued until completed, following which the mixture is allowed to cool to room temperature. The mixture is then extracted with four separate portions of 30 parts of chloroform. The mixture then is acidified with I: concentrated hydrochloric acid to a pH of 2-2.5 and When the procedure of Example I is repeated using 121 parts of cystene instead of iminoacetic acid there is obtained a compound corresponding to the formula 0H CHFCHCDHO CHOHCH, the crystalline solid separated by filtration and recrystal l -NHOHCOOH HgSH lized from water. There is obtained a monomer corresponding to the formula of the monomer of Example XII.

EXAMPLE XIV 163 parts of The procedure of Example I is repeated using 292 parts I:

EXAMPLE XII of divinylbenZene-monoepoxide 75 parts of glycine, and CH H 0 CH 41 parts of NaOH and there is obtained a monomer cora 4 responding to the compound CHnCOOH om=onotmoongr lnom (frH2OHOHgOCgH4GH=CH:

(obtained by treating 1-vinylphenoxy-2,S-epoxypropane which functions as a crosslinking agent as well as a chelating compound. By using the corresponding aminoacids, the following monomers are made in a similar manner.

with ammonia), 144 parts of dimethyl maleate and 300 parts of ethyl ether are mixed and stirred for 150 hours at room temperature, followed by the addition of 50 parts of concentrated hydrochloric acid. The ether layer is separated, dried with anhydrous sodium sulfate and rel onFonotmoomonon, N omonomommon=om CZHg-GHC O OH -OH H0 onponctmoomomlm, N

CHOOOH HzCOOH 1 I filtered. Evaporation of the ether yields the ester,

7 l CHFCHCuHgO 0112011011,

l I -NHCHO o CH3 CHzGOOOHa which :can be used directly as a monomer and thereafter saponified, or it can be saponified directly. 150 parts of this ester is refluxed with 300 parts of water containing 60 parts NaOH for 4 hours, following which it is acidified to a pH of 2.5 with concentrated hydrochloric acid and on cooling, the precipitated monomer is filtered and dried. There is obtained a monomer corresponding to the formula of the monomer of Example VI,

l CH3=CHCuH4OCHrCHCHz I I -NHOHCOOH omooon EXAMPLE XV To a solution containing 120 parts of chloroacetic acid, 100 parts of NaOH, 1000 parts of water is added 163 parts of and the mixture heated at 80-90 C. for 30-45 minutes. A small amount of decolorizing carbon is added and the solution is filtered, then acidified with concentrated hydrochloric acid to a pH of 1.9-2.2, followed by concentrating the solution to 60-70% of its original volume under reduced pressure. The slurry is filtered and the crystals dried. There is obtained a monomer corresponding to the monomer of Example I.

EXAMPLE XVI The monomer of Example XV can be prepared also by reacting the substituted ethanolamine in the presence of alkali with glycolonitrile (or its equivalent formaldehyde and an alkali cyanide) as follows: a mixture of 163 parts of The procedure of Example I is repeated using 176 parts of aminoethyl-aminoacetic acid instead of the iminoacetic acid and there is obtained a monomer corresponding to the formula -o om=onoemoomonom I I umcmnmomo 0 0H):

and when this is treated with chloroacetic acid according to the procedure of Example XV, or with glycolonitrile according to the procedure of Example XVI, there is obtained the monomer corresponding to the formula o om=onotmo 0111011011,

I I -NCH2CH2N(CH:COOH):

CHZGOOH EXAMPLE XVIII The procedure of Example II is repeated using 154 parts of lysine instead of isovaline, and there is obtained a monomer corresponding to the formula [onponotmoomonom I I TNH(CH:)iCHCO-OH and when the monomer is treated with 3 moles of chloroacetic acid according to the procedure of Example XV, or with 3 moles of glycolonitrile according to the procedure of Example XVI, there is obtained the monomer corresponding to the general formula l momoooro; om=onotmoomorrom l l N-omomomomorrooon omoo OH EXAMPLE XIX EXAMPLE XX Fifty parts of distilled water, 0.5 part of hydroxyapatite (0.1 to 0.2 micron), 0.005 part of sodium dodecylbenzenesulphonate, 0.1 part 2,2-azobisisobutyronitrile and 50 parts of l-vinylphenoxy-2,3-epoxypropane are mixed in a suitable quantitative yield of a fusible polymer having the repeating unit,

which is soluble in such solvents as acetone, chloroform,

etc.

EXAMPLE XXI To 1000 parts of water isadded. 25 parts-of CHFCHCdLOCIEhCHCHz I l -N(CH:OOOH):

and the solution maintained at -92" C. for 4 days while exposed to ultraviolet light. There is obtained a precipitate which corresponds to the polymer having -omon- C6H400H1CHOH1 V -N on,oooH

groups.

Using the method of Chaberek and Martell (J. Am. Chem. Soc., 74, 5052 (1952) the disassociation constants as determined qualitatively are about k =4.58 X 10- and k =6.68 10- The polymer turns blue upon the addition of a solution of cupric chloride, leaving the water phase colorless. Using the procedure described by I. Bjerrum (Metal Amine Formation in Aqueous Solution, Publisher Haase and Son, Copenhagen, 1941) it is determined that the polymer forms both 1:1 and 2:1 chelates, whose stability constants are approximately K =5.78 10 and K =1.55 l0 The polymer'also forms chelates with ferric chloride corresponding to 1:1, 1:2, and 1:3 chelates below pH values of 8.6 and the stability constants of these chelates are approximately K =1.26 10 K =4.60 10 and K =8.09 10 13 EXAMPLE. XXII A mixture of 35 parts of [onponoirno OHaOHCHz TNOHzOOOH 100 parts of water, containing 4 parts NaOH are heated to reflux and 50 mg. of sodium persulfate added and the heating continued at 90 C. for 24 hours, following which is added another 50 mg. of sodium persulfate in 200 parts of water and the heating continued for an additional 24 hours. There is obtained a crosslinked polymer gel which is washed with 2000 parts of water. The washed polymer is then added to 2000 parts of dilute sodium hydroxide and the mixture heated, cooled, filtered, washed with 5000 parts water, and dried. There is obtained a crosslinked polymer having the repeating unit,

whose chelate stability constants for copper are approxi- 14 and there is obtained 47.5 parts of a crosslinked polymeric ester which is suspended in '500 parts of 5% sulfuric acid and heated to reflux temperature for 24 hours to hydrolyze the ester groups. There is obtained a chelating polymer having properties similar to that of Example XXV.

EXAMPLE XXVII A mixture of 28 parts of [onponoemo omonom l TNHOHflOOoC/iH5 (the ethyl ester of the monomer of Example V(a') 52 parts of styrene (approximately 1:5 mole ratio of monomers), and 0.35 part of benzoyl peroxide in 200 parts of benzene are refluxed for eight hours and there is obtained a copolymer solution which is concentrated under reduced pressure and the polymer washed with methanol. Hydrolysis of the copolymer with sodium hydroxide produces the sodium salt of the copolymer which on acidification with acid produces the copolymer acid. In a similar manner other ratios of the two monomers from 100:1 to 1:100 can be copolymerized. Also, instead of styrene substituted styrenes, such as the methyl styrenes, the dimethyl styrenes, the chlorostyrenes, etc., may be used to produce the corresponding copolymers.

EXAMPLE XXVIII mately K =2.37 10 and K =4.36 10 26 Parts of EXAMPLE XXIII l A mixture of 25 Parts of om=onoimoomz znoH% I and 81 parts of acrylamide are added to 175 parts of on o FOHCGH' (OHzCOOH): Water and the pH adjusted to 5.5 with NaOH. To this solution is added 0.4 part of 2,2'-azobisisobutyronitrile and 10 parts of and the mixture heated to 70 C. for 10 hours. The reon HO-E onponoomoomonom l ongonomooflmonpon HQCOOH are polymerized by the procedure of Example XXII and there is produced a resinous copolymer which chelates with the metal ions of Fe++, Fe+++, Co++, Ni++, Cu++, Pb++, Mn++, Sr++, and Mn+++.

EXAMPLE XXIV EXAMPLE XXV The procedure of Example XXIV is repeated, using the divinylbenzene-vinylphenoxyepoxypropane copolymer of Example XIX instead of the polymer of Example XX. There is obtained a crosslinked copolymer having chelating properties similar to the polymer of Example JOHII.

EXAMPLE XXVI The procedure of Example XIX is repeated using divinylbenzene and o CHn CHCaH4O omorrom l i TNHCHO O 0 CH3 H700 0 CH3 sulting copolymer is precipitated with acetone, rewashed with acetone, filtered, and dried, and the isolated copolymer forms good chelates with copper and other chelateforming metals. Instead of the approximately 1:1 ratio used above other ratios varying from 1: to 100:1 can be used to prepare chelating copolymers.

XAMPLE XXIX '1000 parts of polyethylene granules are irradiated in air at room temperature with a cobalt 60 source toa dose of 15 magareps and then immersed in a 50% mixture of and heptane and heated at 6070 C. until the increase in weight of the polyethylene is about 25%. The polymer is then hydrolyzed at 80 C. in a 10% NaOH alcohol solution and there is obtained a graft copolymer having chelating proper-ties similar to the polymer of ExampleI.

EXAMPLE XXX An aqueous solution of 2-vinyl phenolate is prepared from parts of 2-viny1 phenol, 42 parts sodium hydroxide, and 400 ml. water. This solution is added with stirring over a period of 1 to 1.5 hours to 102.6 parts of epichlorohydrin at 60 C. and stirred for an addi- 15 tional-hour at 80-85 C. The resulting solution comprises. a

CHg=OHOuH OGH CHCHz which can be used as such,'or the water can be removed by evaporation at reduced pressure. Alternately, the aqueous solution can be extracted with five ZOO-part portions of ethyl ether; the ether removed by'evaporation leaving an oily residue which is distilled at 1 mm. pressure to separate the epoxy compound from a small quantity of l-(2-vinylphenoxy)-2,3-propanediol. When 3- or 4-vinyl phenol are used instead of 2-v-inyl phenol in the above procedure, the corresponding glycidyl ether is obtained. Similarly, when the isopropenyl phenols, or when the vinyl or isopropenyl cresols are used, the corresponding alkenyl aryloxyepoxyalkanes are obtained. When, instead of epi chlorohydrin, there is used other haloepoxyalkanes, such as, for example, 1-chloro-2,3- epoxybutane, 1-chloro-3,4-epoxybutane, 2-chloro -3,4- epoxybutane, l-chloro-Z methyl-2,3-epoxypropane, 1- bromo-2,3-epoxypentane, 2-chloromethyl 1,2-epoxybutane, 1-bromo-4-rnethyl 3,4 epoxypentane, v l-bromo-4- ethyl-2,3-epoxypentane, 4-chloro-2 methyl-2,3-epoxypenlane, 1-chloro-2,3-epoxypentane, 1-chloro-2,3-epoxyoctane, l-chloro-Z-methyl 2,3 epoxyoctane, 1-iodo.-2,3- epoxydecane, etc., then the corresponding alkenylarylepoxyalkane is obtained.

EXAMPLE XXXI A number of the foregoing procedures arerepeated using an equivalent weight of a difierent epoxy compound in place of that of the original example. The following table lists the original example and the respective epoxy compound used. Table H lists the corresponding resulting products.

Table I Example Epoxy compound repeated Table II OH oHFoHmmo-oHmrncH-om 1 NHCHCOOH J HzCOOOH:

CHaCOOH While certain features of this invention have been described in detail with respect to various embodiments thereof, it will, of course, be apparent that other modifications can be made within the spirit and scope of this invention and it is not intended to limit the invention .to the exact details shown above except insofar as they are defined in the following claims.

The invention claimed is:

1. A compound having the formula wherein R is a radical selected from the class consisting of hydrogen and methyl radicals; R is a radical from the class consisting of hydrogen and alkyl radicals of no more than 6 carbon atoms; Ar represents a divalent aromatic radical selected from the class consisting of divalent aromatic hydrocarbon radicals and the chloro, and fluoro derivatives thereof; K is a divalent alkylene radical of at least 1 and no more than 8 carbon atoms in the linear chain between said valencies; and Am represents an aminoacid radical selected from the class consisting of aliphatic aminoacids, the metal and ammonium salts and lower alkyl and lower aryl esters thereof, said Am radical having the valence bond 'of said formula attached to an amino nitrogen in said radical, having no more than about 20 carbon atoms therein and having an amino group no farther than 2 carbon atoms away from a carboxylic group.

2. A polymer having a plurality of repeating units of the formula Ar0-KlOR(l)R2 A m I wherein R is a radical selected from the class consisting of hydrogen and methyl radicals; R is a radical from the class consisting of hydrogen and alkyl radicals of no more than 6 carbon atoms; Ar represents a divalent aromatic radical selected from the class consisting of divalent aromatic hydrocarbon radicals and the chloro, and fluoro derivatives thereof; K is a divalent alkylene radical of at least 1 and no more than 8 carbon atoms in the linear chain between said valencies; and Am represents an aminoacid radical selected from the class consisting ofraliphatic aminoacids, the metal and ammonium salts and lower alkyl and lower aryl esters thereof, said Am radical having the valence bond of said formula attached to an amino nitrogen in said radical, having no more than about 20carbon atoms therein and having an amino group no farther than 2 carbon atoms away from a carboxylic group;

3. A process of preparing chel'ating compounds which comprises the step ofreacting an aminoacid'compound with an alkenylaryloxyepoxyalkane of the formula wherein R' is a radical selected from the class consisting A of hydrogen and methyl radicals; R is a radical from the class consisting of hydrogen and alkyl radicals ofv no more than 6 carbon atoms; Ar represents a divalent aromatic radical selected from the class consisting of divalent aromatic hydrocarbon radicals and the chloro, and fluoro derivatives thereof; and K is a divalent alkylene radical of at least 1 and no more than 8 carbon atoms in the linear chain between said valencies; said aminoacid compound being selected from the class consisting of amino- 10. A compound having the formula om=onoumoonqonc zm ontonomootmoihone i l L omooort acids and the metal and ammonium salts and lower alkyl 11. A compound having the formula and lower aryl esters thereof, said aminoacids having a 20 12. A polymer having a plurality of repeating units hydrogen atom on an amine group therein, having no having the formula more than about 20 carbon atoms therein and having an amino group no farther than 2 carbon atoms away from QH2CH a carboxylic group. l

4. A compound having the formula CsH4OCHzCHGHg l TN(OH2COOH)Q CHFOHCeHm omoHomT l l T h 1 3. Ahpoflymer1 having a plurality of repeating units avm e ormu a 5. A compound having the formula g -011 CH: oHFoHoeHm OHzCHCHz l 1 TNHCCOOH CgH OCH2CHCHz oHeoH, l l TNHCHzOOOH 6. A compound having the formula 14. A polymer of claim 2 having at least 0.1 percent by weight of a polymerizable monomer having at least OH H H OHCH [UHF Ca 400 2 1 al one I-K group copolymerlzed therein.

J 011mm), 15. A polymer of claim 2 having at least 1 percent by weight of divinyl benzene copolymerized therein.

A cII1P11nd having the 'fmmula 16. A process of claim 3 in which the amino-acid is OH iminodiacetic acid. CH,=CHOEH4OCHQCHCH3T 17. A process of claim 3 in which the aminoacid is 1 NHoHeoooH isovaline. 18. A process of claim 3 in which the aminoacid is 8. A compound having the formula glycilm 19. A process of claim 3 in which the aminoacid is CHz=CHCnH4O CHzCHzCHOHzT aspartic acid 1 J-NHOHGOOH 20. A process of claim 3 in which the aminoacid is 011100011 alamne- A compound having the formula References Cited in the file of this patent l UNITED STATES PATENTS E L 2,850,481 DAlelio Sept. 2, 1958 a 2,860,160 Sundberg et al Nov. 11, 1958 

2. A POLYMER HAVING A PLURALITY OF REPEATING UNITS OF THE FORMULA -CH2-CH(-(AR-O-K''-C(-)(-R)-C(-)(-R)2)(-OH)(-AM))WHEREIN R'' IS A RADICAL SELECTED FROM THE CLASS CONSISTING OF HYDROGEN AND METHYL RADICALS; R IS A RADICAL FROM THE CLASS CONSISTING OF HYDROGEN AND ALKYL RADICALS OF NO MORE THAN 6 CARBON ATOMS; AR REPRESENTS A DIVALENT AROMATIC RADICAL SELECTED FROM THE CLASS CONSISTING OF DIVALENT AROMATIC HYDROCARBON RADICALS AND THE CHLORO, AND FLUORO DERIVATIVES THEREOF; K'' IS A DIVALENT ALKYLENE RADICALS OF AT LEAST 1 AND NO MORE THAN 8 CARBON ATOMS IN THE LINEAR CHAIN BETWEEN SAID VALENCIES; AND AM REPRESENTS AN AMINOACID RADICAL SELECTED FROM THE CLASS CONSISTING OF ALIPHATIC AMINOACIDS, THE METAL AND AMMONIUM SALTS AND LOWER ALKYL AND LOWER ARYL ESTERS THEREOF, SAID AM RADICAL HAVING THE VALENCE BOND OF SAID FORMULA ATTACHED TO AN AMINO NITROGEN IN SAID RADICAL, HAVING NO MORE THAN ABOUT 20 CARBON ATOMS THEREIN AND HAVING AN AMINO GROUP NO FARTHER THAN 2 CARBON ATOMS AWAY FROM A CARBOXYLIC GROUP. 